CN107012324A - A kind of method and its system that main accompanying element is reclaimed from cu-ni sulphide ore - Google Patents

A kind of method and its system that main accompanying element is reclaimed from cu-ni sulphide ore Download PDF

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CN107012324A
CN107012324A CN201710229424.9A CN201710229424A CN107012324A CN 107012324 A CN107012324 A CN 107012324A CN 201710229424 A CN201710229424 A CN 201710229424A CN 107012324 A CN107012324 A CN 107012324A
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iron
liquid
nickel
reaction
cobalt
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CN107012324B (en
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赵中伟
李永立
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Central South University
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Central South University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08Sulfuric acid, other sulfurated acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00Obtaining noble metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0026Pyrometallurgy
    • C22B15/0028Smelting or converting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • C22B23/0407Leaching processes
    • C22B23/0415Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043Sulfurated acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • C22B23/0453Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3844Phosphonic acid, e.g. H2P(O)(OH)2
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention provides a kind of method and its system that main accompanying element is reclaimed from cu-ni sulphide ore, this method includes:1) low nickel matte and Leach reaction liquid are continuously added into reaction bottom liquid, Selectively leaching collects hydrogen sulfide gas, the first leachate and first time leached mud, wherein, Leach reaction liquid is the sulfuric acid of mass fraction 60% 95%;2) it is dissolved in water into first time leached mud, collects the second leachate and the second leached mud;3) iron is removed to the second leachate, collects and remove liquid and iron dross removing after iron, except liquid is used for the extraction of nickel and cobalt after iron, iron dross removing is used to smelt iron;And/or, send Copper making device to smelt the second leached mud, respectively obtain copper and noble metal.Method proposed by the present invention can realize the depth separation of ambrose alloy, effectively realize the recovery of nickel, copper, cobalt, noble metal and sulphur.Present invention process is simple, flow is short, efficiency high, is a kind of element recovery process of clean and effective, it is easy to large-scale industrial production.

Description

A kind of method and its system that main accompanying element is reclaimed from cu-ni sulphide ore
Technical field
The present invention relates to non-ferrous metallurgy technology field, master is reclaimed from cu-ni sulphide ore more particularly, to one kind The method and its system of accompanying element.
Background technology
Nickel is a kind of important strategy metal, is widely used in national defence, Aero-Space, communications and transportation, petrochemical industry, the energy Deng field.A considerable amount of nickel minerals are sulphide ores, are associated with copper, cobalt and noble metal (gold, silver and platinum group metal) etc., such as Gansu gold River copper nickel and Yi 1. at Kalatongke, Xingjiang copper nickel.Therefore also need to consider time of cobalt and noble metal while nickel, copper is extracted Receive.
The smelting process of traditional cu-ni sulphide ore is, by matte smelting, to make iron, nickel, cobalt and copper with sulfide shape first Formula is enriched with and forms low nickel matte, and the noble metal of association is also enriched with;Then low nickel matte is bessemerized, by most iron And sulphur is removed, converter mattes are formed.In converting process, the oxidational losses for often resulting in cobalt (about loses 40-60%, it is difficult to return Receive), and generate sulfur dioxide by acid making system obtain industrial sulphuric acid (the problem of sulfuric acid is because of purposes and transportation radius and it is a large amount of Accumulate).Afterwards, the processing method for the converter mattes that blowing is obtained is roughly divided into three classes.
One is, converter mattes carry out the floating separation of mill after slow cooling, respectively obtain low copper nickel sulfide concentrate, low nickel copper sulfide essence Ore deposit and an alloy.Alloy also needs revulcanization-mill is floating to isolate corresponding low copper nickel sulfide concentrate, low nickel copper sulfide essence Ore deposit and secondary alloy.Secondary alloy is used for the recovery of noble metal, and low copper nickel sulfide concentrate is used to extract nickel, but divides because mill is floating From the impurity copper for thoroughly, not also needing to remove carrying subsequently, copper sulfide concentrate is used to carry copper, naturally also has nickel to be taken as impurity The problem of band, cause smelting procedure quite cumbersome.
Second, converter mattes can be also broadly divided into using sour Selectively leaching technique:Low sour pressure leaching or peracid normal pressure leaching Go out.Low sour pressure leaching is in the Fukang Smelter application of China.It is reported that Fukang Smelter is soaked using low sour two sections of adverse currents Go out, be one section of normal pressure leaching (pH >=6.2 for leaching whole liquid) first, next to that one section of pressure leaching, by accurately controlling oxygen Partial pressure makes nickel sulfide Oxidation Leaching, and copper is not leached and (finally give the pH of leachate for 1.8-2.8, oxygen pressure 0.05- 0.06MPa).By obtaining Cu, Fe≤0.01g/L nickel sulfate solution, and copper, your gold in raw material after two sections of counterflow leachings The cobalt of category, iron and sulphur almost all and 40% or so is stayed in nickeliferous 2%-3% finishing slag.And peracid normal pressure leaching most early in Christian pine refinery application, the technique makees leaching agent with the hydrochloric acid (275g/L) of high concentration, and obtained leaching rich solution contains Nickel about 120g/L, hydrochloric acid 160g/L, also each 2g/L of iron, cobalt, copper.About 3% copper is leached, and is largely stayed in slag.So Afterwards after solvent extraction and separation iron, cobalt, copper, make nickel chloride crystallization precipitation through being concentrated by evaporation.In addition, side etc. have studied height to Peng less The dynamics of ice nickel sulfuric acid leaching, and also refer to using two grades of reverse leachings of batch (-type).The Main Ingredients and Appearance Ni of converter mattes2S3With During acid reaction, difficult β-NiS phases are easily generated at a lower temperature, therefore the peracid normal pressure decomposition technique of converter mattes is needed Could effectively it be carried out in the case where temperature is higher than 90 DEG C.
Third, converter mattes also can use the ammonia under the conditions of hyperbaric oxygen to leach.By control the free ammonia content in solution with And oxygen pressure, Cu, Ni and Co is changed into Metal amine complex and is dissolved, while sulphur is oxidized to sulfate radical, noble metal and iron are formed Slag phase is used to reclaim.Free ammonia control is even more important in leaching process, and concentration is low to cause leaching rate low, and excessive concentration can be formed again The high ammino-complex of cobalt, because its is insoluble and caused by cobalt loss.
Three of the above technical thought can handle converter mattes.But problem is that the process for blowing into converter mattes by low nickel matte is worked as In, most cobalt is entered in blowing slag, and a yield of cobalt is low.In addition, because flow is tediously long, about losing 10-20% platinum Race's metal.
To reclaim the cobalt lost in blowing slag, someone will blow slag again through pyrogenic attack, and be reclaimed and be lost by reduction melting Cobalt, reduzate main component be iron-cobalt-nickel alloy and sulfide, as cobalt ice nickel.But it is due to that cobalt is easily oxidized, Content is low, excessively disperses in blowing slag, even if by reduction melting, can only reclaim the cobalt of a part.In addition, this cobalt Ice nickel leach it is extremely complex, need to be through three stages acid leach, first paragraph is mainly the leaching of alloy, in order to prevent copper leaching, it is necessary to Hydrogen sulfide is passed through in leaching process or after leaching or vulcanized sodium is added, the leached mud then formed needs two sections of leaching ability again Obtain cobalt-carrying solution.So, substantial amounts of iron moves in circles in sulphur phase-slag phase, and recovery process is also very cumbersome.
Generally speaking, low nickel matte is blown into converter mattes, though the recovery of cupro-nickel is preferably solved the problems, such as, in association cobalt And there are serious problems in terms of noble metal recovery.And sulphur output in the form of sulfuric acid, market and transportation radius are also to make us head The problem of pain.
Directly handle low nickel matte, it is expected to avoid the valuable element loss of association such as cobalt and noble metal in above-mentioned converting process Problem.But the method for existing processing low nickel matte still has inconvenience when reclaiming associated valuable metals.Sulphation such as low nickel matte is roasted Burning can make nickel cobalt copper be converted into water miscible sulfate, and iron is converted into water-insoluble oxide, and the sulfur dioxide of generation is still used for Relieving haperacidity.But the platinum group metal of association is retained in scum, special Complicated Flow is needed to extract again.Low nickel matte can also pass through Oxygen presses acidleach to handle, such as Yin Fei and Deng Zhilin etc. has made detailed research.But the sulphur of oxidation generation can form retardance Film, influence is leached.In addition during oxygen leaching, considerable amount of iron changes into scum, though be conducive to the nickel and cobalt extraction of postorder, your gold Category is mingled with it to be caused to reclaim difficult.In addition, sulphur is oxidized to sulphur and enters slag phase in leaching process, it is still necessary to further oxidation with Reclaim noble metal.
Generally speaking, existing direct processing low nickel matte has pyrogenic process and the class technique of wet method two.Pyrogenic process can use sulfating roasting, Then reselection leaches valuable element, and iron oxide is stayed in leached mud, but the noble metal in scum reclaims difficult;Many people are blue or green Look at wet method, wet method typically uses oxygen leaching, it is necessary to using autoclave and pure oxygen, but equally faces your gold is reclaimed from scum The problem of category, and sulphur is oxidized to sulphur formation parcel during acid oxygen leaching, and noble metal reclaims the difficulty that remains unchanged.
The content of the invention
(1) technical problem to be solved
The technical problem to be solved in the present invention is can not effectively to realize each element in existing cu-ni sulphide ore smelting process Reclaim, the rate of recovery of particularly element cobalt and noble metal is too low.
(2) technical scheme
In order to solve the above-mentioned technical problem, the invention provides a kind of side that main accompanying element is reclaimed from cu-ni sulphide ore Method, including:
1) low nickel matte and Leach reaction liquid that cu-ni sulphide ore is obtained through matte smelting are continuously added into reaction bottom liquid, selected Selecting property is leached, and hydrogen sulfide gas, the first leachate and first time leached mud are collected respectively, wherein, reaction bottom liquid is quality Fraction 20%-60% sulfuric acid solution, the Leach reaction liquid is mass fraction 60%-95% sulfuric acid solution;
2) water is added into the first time leached mud, dissolves, the second leachate and the second leached mud are collected respectively;
3) to second leachate carry out remove iron, respectively collect remove iron after liquid and iron dross removing, it is described remove iron after liquid be used for The extraction of nickel and cobalt, the iron dross removing is used to smelt iron;
And/or, send Copper making device to smelt second leached mud, respectively obtain copper and noble metal.
In the present invention, the low nickel matte that cu-ni sulphide ore is obtained through matte smelting is directly handled using high-concentration sulfuric acid, profit With nickel, cobalt, iron sulfate in high-concentration sulfuric acid solution the low characteristic of solubility, make they crystallize precipitations enter slag phase, enter And filtering is achieved that and separated with high-concentration sulfuric acid solution.
In a preferred embodiment of the invention, Leach reaction liquid is preferably the sulfuric acid that mass fraction is 85%-90% Solution.
In leaching process, cuprous sulfide and noble metal are not involved in reaction, also together stay in slag.Containing nickel, cobalt, iron sulphur The leached mud of hydrochlorate crystal, cuprous sulfide and noble metal dissolves sulfate by the leaching that adds water, and can just be vulcanized after filtering The secondary filter residue of cuprous and noble metal and containing nickel, cobalt, iron sulfate the aqueous solution.Then secondary filter residue send copper metallurgy industry to return Receive copper and noble metal.Nickel cobalt iron rule is through except extract and separate nickel cobalt just can obtain corresponding product again after iron.
In addition, the part sulfur dioxide obtained during matte smelting and the hydrogen sulfide gas generated in leaching process are anti- Should, high-purity sulphur can be prepared, is readily transported and stores;Remaining sulfur dioxide enters sulfate system and prepares sulfuric acid as leaching agent.
In the present invention, directly processing cu-ni sulphide ore can avoid low nickel matte through the low nickel matte obtained by matte smelting after In sequence tradition converting process technique the problem of the association such as cobalt and noble metal valuable element loss.The present invention utilizes the sulfuric acid of iron nickel cobalt Salt is crystallized from leachate because of saturation and separated out, and realizes the separation with high-concentration sulfuric acid.Filter residue through it is simple it is water-soluble after again Realize the separation of copper and iron nickel cobalt.
Use sulfuric acid direct to low nickel matte carries out normal pressure Selectively leaching, and under the concentration and liquid-solid ratio, ferronickel cobalt is molten In sulfuric acid solution, and completely reaction generation hydrogen sulfide gas, now, in low nickel matte cuprous sulfide and noble metal almost regardless of Solution, you can the depth separation of ambrose alloy is realized in leaching process.
Meanwhile, copper and noble metal are effectively stayed in into the second leached mud using above-mentioned leaching step, then the leached mud is sent Copper metallurgy industry is smelted, and now noble metal moves towards single, can effectively reclaim, and improves the cobalt and platinum family of association in cu-ni sulphide ore Metal recovery rate.
Low nickel matte is mainly derived from cupro-nickel vulcanised ore concentrate, and main component is Ni5Fe4S8, in addition to nickel simultaneously rich in copper, cobalt and A large amount of platinum families need to reclaim, method of the invention be more suitable for decomposition of the cu-ni sulphide ore through low nickel matte made from matte smelting with Extract.
Those skilled in the art can select to carry out phase to the second leachate or the second leached mud according to actual needs The processing answered, the accompanying elements such as nickel, cobalt, iron, copper and noble metal are separately recovered.
In actual mechanical process, typically Leach reaction is placed in reactor, i.e. step 1) can be:
Into reactor, the sulfuric acid solution of filling reaction bottom liquid, i.e. mass fraction 20%-60%, is used as reaction bottom liquid;Together When low nickel matte and Leach reaction liquid mass fraction 60%-95% sulfuric acid solution added into reactor reacted.
In a preferred embodiment, in order that the sulfate of iron nickel cobalt crystallizes analysis because of saturation from Leach reaction liquid Go out, Leach reaction liquid and low nickel matte are continuously added to, and in maintenance reaction kettle sulfuric acid consumption it is consistent with addition, lasting charging Reacted.
In a preferred embodiment of the invention, in order that reaction more completely and is easy to control reaction end solution Sulfuric acid concentration, the reaction bottom liquid that total kettle accumulates 30%-60%, i.e. mass fraction 20%-60% are generally filled with into reactor Sulfuric acid solution.
In a preferred embodiment of the invention, continue to leach 0.5-2h after the completion of typically feeding.It is being preferable to carry out In mode, Ke Yiwei:Until stopping charging when slurry reaches the 80% of total kettle product in reactor, continue to react 0.5-2h, and Collect hydrogen sulfide gas, the first leachate and the first leached mud of course of reaction generation.
In a preferred embodiment of the invention, in order that step 1) in leaching it is more complete so that ambrose alloy It is kept completely separate, Selectively leaching, which is that normal pressure is non-oxidizable, to be leached, and without extra firing equipment, with low nickel matte and 60%- 95% sulfuric acid is continuously added into, and solution reaction temperature can be warming up to 80-100 DEG C.
In a preferred embodiment of the invention, the hydrogen sulfide gas collected after Selectively leaching can be melted with making sulfonium The sulfur dioxide produced in refining send sulfur system to prepare sulphur, and unnecessary sulfur dioxide send sulfate system to prepare sulfuric acid for matching somebody with somebody Sulfuric acid solution, i.e. Leach reaction liquid and reaction bottom liquid.In the preferred embodiment of the present invention, by the sulfur dioxide one of generation Relieving haperacidity is divided to be used as leaching agent, a part and the hydrogen sulfide reaction of generation generate sulphur, so as to solve a large amount of sulphur in traditional handicraft The accumulation problem of acid.In addition, low nickel matte hydrogen sulfide gas produced during sulfuric acid leaching is used to prepare sulphur by the present invention Sulphur, can solve the problem of outlet of the sulphur of long-standing problem nickel sulfide ore enterprise, with sulphur in conventional method to the sulfuric acid for preparing Situation is more easily than storage and transported.
After the first leachate and the first leached mud is obtained, wherein, the first leachate is reclaimed and returned as reaction bottom liquid Return reactor and handle next batch materials, recycle, substantially reduce acid consumption and the pollution to environment, and metal recovery can be improved Rate.
In step 2) in, the first leached mud can be pumped into the dissolving tank containing deionized water, now, in Leach reaction mistake Secondary filter after nickel sulfate, cobalt sulfide and the errous sulfate crystal separated out in journey by supersaturation dissolves again, is collected respectively The second leachate containing nickel sulfate, cobaltous sulfate and ferrous sulfate and the second leaching for being enriched with cuprous sulfide and noble metal Slag.
In the present invention, can be to step 3) the second leachate carries out removing iron using method for removing iron commonly used in the art, In order to be able to preferably remove iron and do not influence the rate of recovery of nickel cobalt, in a preferred embodiment of the invention, it is preferred to use pin Iron ore method or hematite process.
Copper content is less than 0.009g/L, preferably smaller than 0.003g/L, now, iron in solution in the second leachate in the present invention Mainly exist in ferrous ion form, without again through reduction can direct oxidation form goethite or bloodstone and remove, i.e., one In individual preferred embodiment, the gas (such as air or pure oxygen) rich in oxygen can be passed through into leachate, obtains removing liquid after iron And iron dross removing.
Second leachate can be placed in enclosed high pressure kettle, logical pure oxygen is simultaneously warming up to 200 DEG C, and iron is removed in bloodstone form Go, obtain removing liquid and iron dross removing after iron.
Also can be to the second leachate blowing air or oxygen-enriched air, while the pH for maintaining solution is 3-4, you can by iron with pin iron Ore deposit form is removed, and obtains removing liquid and iron dross removing after iron.
Obtained scum can be fired into iron ore concentrate, for smelting iron.
Except liquid can be used method commonly used in the art and realize the extraction of nickel and cobalt after iron, in order to fully achieve the present invention The extraction of middle nickel and cobalt, in a preferred embodiment, by the pH except liquid after iron be adjusted to 4.0-5.5 remove backward after iron in liquid plus Enter extractant, extract and separate obtains cobalt-carrying solution and solution containing nickel, then the pH of solution containing nickel is adjusted to 5.5-7.0 and use extractant Carry out the extraction of nickel;
Wherein, the extractant is P507 kerosin or Cyanex272 kerosin, and volume fraction is 10- 50%.In above-mentioned extractant, kerosene is diluent.
Wherein, P507 is di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester, and Cyanex272 is two (2,4,4- trimethyls penta Base) hypophosphorous acid.
When extractant is P507 kerosin, the pH except liquid after iron is adjusted to 4.0-5.0, then add in liquid to after except iron Enter extractant, extract cobalt with extractant, extract and separate obtains cobalt-carrying solution and solution containing nickel, then the pH of solution containing nickel is adjusted to 5.5-6.5, uses extractant extraction of nickel, hydrochloric acid back extraction obtains nickel chloride solution, for preparing nickel product.Wherein, by cobalt-carrying solution Cobalt chloride solution is obtained with hydrochloric acid back extraction, for preparing cobalt product.
When extractant is Cyanex272 kerosin, the pH except liquid after iron is adjusted to 5.0-5.5, then to after except iron Extractant is added in liquid, extract and separate obtains cobalt-carrying solution and solution containing nickel, then the pH of solution containing nickel is adjusted into 6.5-7.0, used Extractant extraction of nickel, sulfuric acid back extraction obtains nickel sulfate solution, for preparing nickel sulfate product.Wherein, by cobalt-carrying solution sulfuric acid Back extraction obtains cobalt sulfate solution, for preparing cobaltous sulfate product.
In a preferred embodiment of the invention, copper can be obtained and expensive using Copper making method conventional in the art Metal, in order that copper and noble metal are kept completely separate, in a preferred embodiment of the invention, be preferably:
By the second leached mud through bessemerizing obtained blister copper, then respectively obtain through electrolysis the anode of refined copper and enriching noble metals Mud, the earth of positive pole is used to extract noble metal.
Or, Ore Leaching will be used after the oxidized roasting of the second leached mud, the leachate of enriching Cu is collected respectively and is enriched with expensive The leached mud of metal, leached mud is used to extract noble metal.
Or, the second leached mud is subjected to oxygen leaching, the leaching of the leachate and enriching noble metals of enriching Cu is collected respectively Slag, leached mud is used to extract noble metal.
The leaching rate of nickel, iron, cobalt is more than 99% obtained by the method for the present invention, and cobalt and noble metal have been obtained effectively Reclaim, the rate of recovery of copper is more than 98%, and the rate of recovery of noble metal is more than 95%.
According to a further aspect of the present invention, a kind of system that main accompanying element is reclaimed from cu-ni sulphide ore is additionally provided, Including:
Selectively leaching device, with low nickel matte and the respective continuous charging mouthful of Leach reaction liquid, Selectively leaching device In containing reaction bottom liquid, and cause to reaction bottom liquid in be continuously added into low nickel matte and the leaching that cu-ni sulphide ore is obtained through matte smelting Selectively leaching reaction occurs when going out reaction solution;The Selectively leaching the device also collection device including hydrogen sulfide gas, the The collection device of one leachate and the collection device of first time leached mud, wherein, reaction bottom liquid is mass fraction 20%-60%'s Sulfuric acid solution, Leach reaction liquid is mass fraction 60%-95% sulfuric acid solution;
Water dissolver, for dissolving first time leached mud using water, collects the second leachate and second is leached respectively Slag;
Deironing apparatus, second of leachate for will be obtained in water dissolver carries out removing iron;
The extraction element of nickel and cobalt, liquid, the extraction for nickel and cobalt after iron are removed for collecting in deironing apparatus;
Iron-smelting device, for collecting the iron dross removing in deironing apparatus, for smelting iron;
And/or, Copper making device, for second leached mud to be carried out into Copper making, respectively obtains copper and noble metal.
In a preferred embodiment of the invention, also include in system:
Sulphur preparation facilities, for sulfur dioxide and the normal pressure selective leaching for making to produce in the matte smelting device Go out in device to produce hydrogen sulfide gas reaction completely and sulphur is made;
Sulfuric acid preparation facilities, for the remaining sulfur dioxide produced in the matte smelting device to be converted into sulfuric acid, and Provide it to the normal pressure Selectively leaching device.
In a preferred embodiment of the invention, the first leaching liquor collecting device can be additionally used in selective leaching in system Go out device and reaction bottom liquid is provided.
The method of the present invention preferably uses the system of the present invention to realize.
A kind of method and its system that main accompanying element is reclaimed from cu-ni sulphide ore proposed by the present invention, using nickel, iron, The vitriol of the cobalt characteristic that solubility declines in peracid, at certain acidity bottom, (i.e. mass fraction is 20%-60%'s to liquid Sulfuric acid solution) in the presence of, use low nickel matte and Leach reaction liquid (i.e. mass fraction for 60%-95% sulfuric acid solution) simultaneously The pattern for the successive reaction that feeds so that nickel, iron, the sulfate of cobalt of generation are separated out because of saturation;The first-time filtrate being filtrated to get Bottom liquid recycling can be done;One time filter residue contains the nickel sulfate separated out by saturation, cobaltous sulfate and ferric sulfate crystal, and is difficult to By the cuprous sulfide and noble metal of sulfuric acid leaching, the sulfate solution of nickel, cobalt, iron is obtained after water-soluble, and is enriched with expensive The cuprous sulfide slag of metal, while can realize that copper and the depth of nickel, cobalt, iron are separated;Nickel, cobalt, the sulfate solution of iron are through removing It is used for the extraction of nickel sulfate and cobaltous sulfate after iron;The cuprous sulfide slag for being enriched with noble metal is returned through traditional Copper making and noble metal Sequence of knocking off can effectively reclaim copper and noble metal.And the sulfur dioxide reaction that the hydrogen sulfide gas generated is generated with matte smelting is made Standby high-purity sulphur, is readily transported and deposits.This method flow is short, efficiency high, can not only realize the depth separation of ambrose alloy, also Be conducive to greatly improving the rate of recovery of cobalt and noble metal, be a kind of element comprehensive utilization process of clean and effective, it is easy to be extensive Industrial production.
Brief description of the drawings
Fig. 1 be according in the embodiment of the present invention 1 to reclaiming nickel, cobalt, iron, noble metal, copper and sulphur from cu-ni sulphide ore The schematic flow sheet of the method for element.
Embodiment
With reference to the accompanying drawings and examples, the embodiment to the present invention is described in further detail.Implement below Example is used to illustrate the present invention, but is not limited to the scope of the present invention.
Embodiment 1
As shown in figure 1, in the present embodiment, cu-ni sulphide ore obtains low nickel matte, essential element content after matte smelting:Ni 20.21%, Cu 10.52%, Fe37.44%, Co 0.78%, noble metal about 10g/t, while there is sulfur dioxide generation.
With Sulphuric acid mass fraction reaction bottom liquid is used as 30% solution;It is simultaneously 90% with Sulphuric acid mass fraction Solution is used as Leach reaction liquid.The reaction bottom liquid of total kettle product 40% is filled into reactor;Added simultaneously into reactor low Ice nickel and reaction leachate reacted, and in maintenance reaction kettle sulfuric acid consumption it is consistent with addition;Lasting charging is carried out Reaction, until stopping charging when slurry reaches the 80% of total kettle product in reactor, continues to react 1h, and collect course of reaction life Into hydrogen sulfide gas.
Slurry after the completion of reaction is cooled to after room temperature and filtered, and respectively obtains first-time filtrate and a filter residue, wherein First-time filtrate is used as the reaction bottom liquid leached next time;Filter residue is then pumped into the dissolving tank containing deionized water, question response process Secondary filter after the middle nickel sulfate separated out by saturation, cobalt sulfide and errous sulfate crystal dissolve again, is obtained containing sulfuric acid Nickel, the secondary filtrate of cobaltous sulfate and ferrous sulfate and the secondary filter residue for being enriched with cuprous sulfide and noble metal, realize copper with The separation of nickel cobalt.Filter copper content in resulting solution and be less than 0.003g/L, iron mainly exists in ferrous ion form, maintained molten Liquid pH is 3-4, is passed directly into air and is aoxidized, and without again removing through reduction, iron formation goethite, gained scum is fired into Iron ore concentrate, available for smelting iron.Except liquid adjusts pH to 4 after iron, cobalt is extracted with P507, cobalt chloride solution is obtained with hydrochloric acid back extraction, uses In preparing cobalt product.PH value of solution is adjusted again to 5.5, uses P507 extraction of nickel, hydrochloric acid back extraction obtains nickel chloride solution, for preparing nickel Product.
Secondary filter residue is the cuprous sulfide for being enriched noble metal, and main component is:Ni 0.49%, Cu 73.2%, Fe 0.72%, Co < 0.009%, noble metal about 67g/t (leaching rate of equivalent ferronickel cobalt is more than 99%), are directly bessemerized Blister copper is prepared, blister copper obtains refined copper through electrorefining again, and noble metal is then enriched in the earth of positive pole, send noble metal systems to reclaim, its In, the rate of recovery of copper is up to more than 98%, and the rate of recovery of noble metal is up to more than 95%.A part of dioxy of matte smelting process Change sulphur and prepare sulphur with hydrogen sulfide reaction, its consumption is 1/2nd of hydrogen sulfide mole;Remaining sulfur dioxide send sulfuric acid System extracting sulfuric acid, for reaction bottom liquid and Leach reaction liquid.
Embodiment 2
Cu-ni sulphide ore obtains low nickel matte, essential element content after matte smelting:Ni 13.25%, Cu 8.32%, Fe 38.44%, Co 0.64%, noble metal about 8g/t, while there is sulfur dioxide generation.
With Sulphuric acid mass fraction reaction bottom liquid is used as 40% solution;It is simultaneously 85% with Sulphuric acid mass fraction Solution is used as Leach reaction liquid.The reaction bottom liquid of total kettle product 45% is filled into reactor;Added simultaneously into reactor low Ice nickel and reaction leachate reacted, and in maintenance reaction kettle sulfuric acid consumption it is consistent with addition;Lasting charging is carried out Reaction, until stopping charging when slurry reaches the 80% of total kettle product in reactor, continues to react 1.5h, and collect course of reaction The hydrogen sulfide gas of generation.
Slurry after the completion of reaction is cooled to after room temperature and filtered, and respectively obtains first-time filtrate and a filter residue, wherein First-time filtrate is used as the reaction bottom liquid leached next time;Filter residue is then pumped into the dissolving tank containing deionized water, question response process Secondary filter after middle nickel sulfate, cobalt sulfide and the errous sulfate crystal separated out by supersaturation dissolves again, is obtained containing sulphur Sour nickel, the secondary filtrate of cobaltous sulfate and ferrous sulfate and the secondary filter residue for being enriched with cuprous sulfide and noble metal, realize copper With the separation of nickel cobalt.Filter copper content in resulting solution and be less than 0.009g/L, iron mainly exists in ferrous ion form, by this Solution is placed in enclosed high pressure kettle, and logical pure oxygen is simultaneously warming up to 180 DEG C, by iron with the removing of bloodstone form.Except liquid adjusts pH after iron To 5, cobalt is extracted with P507, cobalt sulfate solution is obtained with sulfuric acid back extraction, for preparing cobalt product.PH value of solution is adjusted again to 6.5, is used P507 extraction of nickel, sulfuric acid back extraction obtains nickel sulfate solution, for preparing nickel product.
Secondary filter residue is the cuprous sulfide for being enriched noble metal, and main component is:Ni 0.16%, Cu 72.6%, Fe 0.95%, Co < 0.007% (leaching rate of equivalent ferronickel cobalt is more than 99%), noble metal about 65g/t be (equivalent ferronickel cobalt Leaching rate is more than 99%).Sulfuric acid leaching is used after oxidized roasting, the leaching of copper-bath and enriching noble metals is obtained Slag, the leached mud of enriching noble metals send noble metal systems to reclaim, wherein, the rate of recovery of copper is up to more than 98%, time of noble metal Yield is up to more than 95%.A part of sulfur dioxide of matte smelting process prepares sulphur with hydrogen sulfide reaction, and its consumption is sulphur Change 1/2nd of hydrogen mole;Remaining sulfur dioxide send sulfate system extracting sulfuric acid, for anti-with reaction bottom liquid and leaching Answer liquid.
Embodiment 3
Cu-ni sulphide ore obtains low nickel matte, essential element content after matte smelting:Ni 16.55%, Cu 10.32%, Fe 33.44%, Co 0.34%, noble metal about 11g/t, while there is sulfur dioxide generation.
With Sulphuric acid mass fraction reaction bottom liquid is used as 20% solution;It is simultaneously 60% with Sulphuric acid mass fraction Solution is used as Leach reaction liquid.The reaction bottom liquid of total kettle product 30% is filled into reactor;Added simultaneously into reactor low Ice nickel and reaction leachate reacted, and in maintenance reaction kettle sulfuric acid consumption it is consistent with addition;Lasting charging is carried out Reaction, until stopping charging when slurry reaches the 80% of total kettle product in reactor, continues to react 0.5h, and collect course of reaction The hydrogen sulfide gas of generation.
Slurry after the completion of reaction is cooled to after room temperature and filtered, and respectively obtains first-time filtrate and a filter residue, wherein First-time filtrate is used as the reaction bottom liquid leached next time;Filter residue is then pumped into the dissolving tank containing deionized water, question response process Secondary filter after middle nickel sulfate, cobalt sulfide and the errous sulfate crystal separated out by supersaturation dissolves again, is obtained containing sulphur Sour nickel, the secondary filtrate of cobaltous sulfate and ferrous sulfate and the secondary filter residue for being enriched with cuprous sulfide and noble metal, realize copper With the separation of nickel cobalt.Filter copper content in resulting solution and be less than 0.006g/L, iron mainly exists in ferrous ion form, maintained PH value of solution is 3-4, and the oxygen-enriched air for being passed directly into 30%-50% is aoxidized, without again removing through reduction, iron formation goethite Go, gained scum is fired into iron ore concentrate, available for smelting iron.Except liquid adjusts pH to 5 after iron, cobalt is extracted with Cyanex272, hydrochloric acid is used Back extraction obtains cobalt chloride solution, for preparing cobalt product.PH value of solution is adjusted again to 6.5, then uses Cyanex272 extraction of nickel, hydrochloric acid Back extraction obtains nickel chloride solution, for preparing nickel product.
Secondary filter residue is the cuprous sulfide for being enriched noble metal, and main component is:Ni 0.12%, Cu 76.4%, Fe 0.62%, Co < 0.008% (leaching rate of equivalent ferronickel cobalt is more than 99%), noble metal about 78g/t be (equivalent ferronickel cobalt Leaching rate is more than 99%), using autoclave oxygen leaching, obtaining copper-containing solution is used for copper processed, and leached mud is then used to reclaim Noble metal, wherein, the rate of recovery of copper is up to more than 98%, and the rate of recovery of noble metal is up to more than 95%.Matte smelting process A part of sulfur dioxide prepares sulphur with hydrogen sulfide reaction, and its consumption is 1/2nd of hydrogen sulfide mole;Remaining dioxy Change sulphur and send sulfate system extracting sulfuric acid, for reaction bottom liquid and Leach reaction liquid.
Embodiment 4
Cu-ni sulphide ore obtains low nickel matte, essential element content after matte smelting:Ni 12.55%, Cu 8.32%, Fe 39.44%, Co 0.24%, noble metal about 10.8g/t, while there is sulfur dioxide generation.
With Sulphuric acid mass fraction reaction bottom liquid is used as 60% solution;It is simultaneously 95% with Sulphuric acid mass fraction Solution is used as Leach reaction liquid.The reaction bottom liquid of total kettle product 60% is filled into reactor;Added simultaneously into reactor low Ice nickel and reaction leachate reacted, and in maintenance reaction kettle sulfuric acid consumption it is consistent with addition;Lasting charging is carried out Reaction, until stopping charging when slurry reaches the 80% of total kettle product in reactor, continues to react 2h, and collect course of reaction life Into hydrogen sulfide gas.
Slurry after the completion of reaction is cooled to after room temperature and filtered, and respectively obtains first-time filtrate and a filter residue, wherein First-time filtrate is used as the reaction bottom liquid leached next time;Filter residue is then pumped into the dissolving tank containing deionized water, question response process Secondary filter after middle nickel sulfate, cobalt sulfide and the errous sulfate crystal separated out by supersaturation dissolves again, is obtained containing sulphur Sour nickel, the secondary filtrate of cobaltous sulfate and ferrous sulfate and the secondary filter residue for being enriched with cuprous sulfide and noble metal, realize copper With the separation of nickel cobalt.Filter copper content in resulting solution and be less than 0.004g/L, iron mainly exists in ferrous ion form, without The solution, is directly placed in enclosed high pressure kettle by reduction, and logical pure oxygen is simultaneously warming up to 220 DEG C, by iron with the removing of bloodstone form.Remove Liquid adjusts pH to 5.5 after iron, and cobalt is extracted with Cyanex272, cobalt sulfate solution is obtained with sulfuric acid back extraction, for preparing cobalt product. PH value of solution is adjusted again to 7, then uses Cyanex272 extraction of nickel, and sulfuric acid back extraction obtains nickel sulfate solution, for preparing nickel product.
Secondary filter residue is the cuprous sulfide for being enriched noble metal, and main component is:Ni 0.11%, Cu 72.3%, Fe 0.40%, Co < 0.004% (leaching rate of equivalent ferronickel cobalt is more than 99%), noble metal about 75g/t be (equivalent ferronickel cobalt Leaching rate is more than 99%), using autoclave oxygen leaching, obtaining copper-containing solution is used for copper processed, and leached mud is then used to reclaim Noble metal, wherein, the rate of recovery of copper is up to more than 98%, and the rate of recovery of noble metal is up to more than 95%.Matte smelting process A part of sulfur dioxide prepares sulphur with hydrogen sulfide reaction, and its consumption is 1/2nd of hydrogen sulfide mole;Remaining dioxy Change sulphur and send sulfate system extracting sulfuric acid, for reaction bottom liquid and Leach reaction liquid.
Finally, method of the invention is only preferably embodiment, is not intended to limit the scope of the present invention.It is all Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements made etc. should be included in the protection of the present invention Within the scope of.

Claims (10)

1. a kind of method that main accompanying element is reclaimed from cu-ni sulphide ore, including:
1) low nickel matte and Leach reaction liquid that cu-ni sulphide ore is obtained through matte smelting are continuously added into reaction bottom liquid, selectivity Leach, hydrogen sulfide gas, the first leachate and first time leached mud are collected respectively, wherein, reaction bottom liquid is mass fraction 20%-60% sulfuric acid solution, the Leach reaction liquid is mass fraction 60%-95% sulfuric acid solution;
2) water is added into the first time leached mud, dissolves, the second leachate and the second leached mud are collected respectively;
3) to second leachate carry out remove iron, respectively collect remove iron after liquid and iron dross removing, it is described remove iron after liquid be used for nickel and The extraction of cobalt, the iron dross removing is used to smelt iron;
And/or, send Copper making device to smelt second leached mud, respectively obtain copper and noble metal.
2. according to the method described in claim 1, it is characterised in that the Selectively leaching, which is that normal pressure is non-oxidizable, to be leached;
And/or, the Leach reaction liquid is the sulfuric acid solution that mass fraction is 85%-90%.
3. method according to claim 1 or 2, it is characterised in that the low nickel matte and Leach reaction liquid are simultaneously continuous to be added Enter, and both additions are identical with consumption;
First leachate returns to the reaction bottom liquid as next batch materials, recycles.
4. the method according to any one of claim 1-3, it is characterised in that in step 1) in, continue after the completion of charging Leach 0.5-2h.
5. the method according to any one of claim 1-4, it is characterised in that the titanium dioxide produced in the matte smelting Sulphur and step 1) in stink damp precursor reactant prepare sulphur, and remaining sulfur dioxide is converted into step 1) in carry out normal pressure Sulfuric acid solution used in Selectively leaching.
6. the method according to any one of claim 1-5, it is characterised in that the step 3) in leached to described second Liquid is carried out except iron is specially:
The gas rich in oxygen is passed through into the second leachate, obtains removing liquid and iron dross removing after iron.
7. the method according to any one of claim 1-6, it is characterised in that the step 3) described in remove liquid after iron and use It is specially in the extraction of nickel and cobalt:
Liquid pH after iron will be removed to be adjusted to after 4.0-5.5, extractant is added in liquid to after except iron, extract and separate obtains cobalt-carrying solution and contained Nickel solution, then the pH of solution containing nickel is adjusted to the extraction that 5.5-7.0 carries out nickel using the extractant;
Wherein, the extractant is P507 kerosin or Cyanex272 kerosin, and volume fraction is 10-50%.
8. the method according to any one of claim 1-7, it is characterised in that the recovery method tool of the copper and noble metal Body is:
By the second leached mud through bessemerizing obtained blister copper, then respectively obtain through electrolysis the earth of positive pole of refined copper and enriching noble metals, The earth of positive pole is used to extract noble metal;
Or, Ore Leaching will be used after the oxidized roasting of the second leached mud, the leachate and enriching noble metals of enriching Cu are collected respectively Leached mud, leached mud be used for extract noble metal;
Or, the second leached mud is subjected to oxygen leaching, the leachate of enriching Cu and the leached mud of enriching noble metals, leaching are collected respectively Slag tap for extracting noble metal.
9. a kind of system that main accompanying element is reclaimed from cu-ni sulphide ore, including:
Selectively leaching device, with low nickel matte and the respective continuous charging mouthful of Leach reaction liquid, the Selectively leaching device In containing reaction bottom liquid, and cause to reaction bottom liquid in be continuously added into low nickel matte and the leaching that cu-ni sulphide ore is obtained through matte smelting Selectively leaching reaction occurs when going out reaction solution;The Selectively leaching the device also collection device including hydrogen sulfide gas, the The collection device of one leachate and the collection device of first time leached mud, wherein, reaction bottom liquid is mass fraction 20%- 60% sulfuric acid solution, the Leach reaction liquid is mass fraction 60%-95% sulfuric acid solution;
Water dissolver, for dissolving first time leached mud using water, collects the second leachate and second of leached mud respectively;
Deironing apparatus, second of leachate for will be obtained in water dissolver carries out removing iron;
The extraction element of nickel and cobalt, liquid, the extraction for nickel and cobalt after iron are removed for collecting in deironing apparatus;
Iron-smelting device, for collecting the iron dross removing in deironing apparatus, for smelting iron;
And/or, Copper making device, for second leached mud to be carried out into Copper making, respectively obtains copper and noble metal.
10. system according to claim 9, it is characterised in that also include:
Sulphur preparation facilities, for will be produced in the sulfur dioxide produced in matte smelting and the normal pressure Selectively leaching device Sulphur is made in stink damp precursor reactant;
Sulfuric acid preparation facilities, for the part produced in matte smelting sulfur dioxide to be converted into sulfuric acid, and provides it to institute State normal pressure Selectively leaching device.
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CN107604170A (en) * 2017-08-25 2018-01-19 金川集团股份有限公司 A kind of method of separation and concentration noble metal in potassium cloride slag from low nickel matte
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